JP2018145482A - Abrasion-resistant coating, formation method thereof, and abrasion-resistant member - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an abrasion-resistant coating capable of maintaining excellent abrasion resistance over an extended period, even when abrasion to slip or the like is repeated, and also excellent in adhesion; and to provide a manufacturing method thereof, and an abrasion-resistant member.SOLUTION: An abrasion-resistant coating 10 has a plating layer 11, and a lubricant layer 12 laminated on the plating layer 11, in which the lubricant layer 12 contains a solid lubricant 2. A formation method of the abrasion-resistant coating includes the first step for laminating the plating layer 11 by subjecting a substrate 20 surface to a plating treatment, and the second step for laminating the lubricant layer 12 containing the solid lubricant 2 on the surface of the plating layer 11.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a wear-resistant film, a method for forming the same, and a wear-resistant member.

  Conventionally, it has been required to impart excellent wear resistance to various mechanical parts, tools, molds, and other members, and various techniques have been studied. Particularly in recent years, for example, the wear resistance against slipping of various members has been improved by forming a film having excellent wear resistance on the surface of the member by a method such as plating.

  For example, Patent Document 1 discloses a technique for preventing wear caused by slippage in a pulley for a continuously variable transmission and a belt-type continuously variable transmission by providing irregularities on the pulley surface that the belt contacts. Further, Patent Document 1 discloses that the unevenness is plated, and thereby attempts to improve wear resistance against slipping.

  Patent Document 2 discloses a technique for forming a microporous or microcracked chromium plating film on a bearing surface of a rolling bearing. Such a chromium plating film can hold the self-lubricating resin by the microporous or microcrack existing on the surface thereof, thereby making the shaft easy to slide on the bearing surface and improving the wear resistance against sliding. Yes.

JP 2012-117579 A Japanese Patent Laid-Open No. 2006-180439

  However, the conventional wear-resistant film can certainly improve the wear resistance against slipping of various members, but if wear is repeated over a long period of time, the film may be scraped or deteriorated. It has been a problem that the phenomenon progresses gradually, causing a decrease in wear resistance. For example, as in the technique disclosed in Patent Document 1, merely by providing irregularities on the surface of the substrate, the wear resistance against slipping gradually decreases, and the plating film formed on the irregularities also gradually peels off. Is easily damaged over time. Further, even with the method of Patent Document 2, the self-lubricating resin held in the microcracks or the like is eventually peeled off and disappears, so that it is difficult to maintain the wear resistance against slipping for a long time. Furthermore, in the techniques disclosed in Patent Documents 1 and 2, the adhesion between the plating film and the base material and the adhesion between the self-lubricating resin and the base material surface are also poor due to repeated long-term sliding wear. It was a factor that the film easily peeled off.

  In recent years, with regard to the wear resistance of various members, there is a need for a wear-resistant film that can maintain excellent wear resistance over a long period of time even if wear is repeated. There was a need for further improvement.

  The present invention has been made in view of the above, for example, it is possible to maintain excellent wear resistance over a long period of time even if wear against slipping or the like is repeated, and a wear-resistant film excellent in adhesion and a method for producing the same, An object of the present invention is to provide a wear-resistant member.

  As a result of intensive studies to achieve the above object, the present inventor has found that the above object can be achieved by forming the film into a specific layer structure, and has completed the present invention.

That is, the present invention includes, for example, the inventions described in the following sections.
Item 1. Having a plating layer and a lubricating layer laminated on the plating layer;
The lubricating layer is a wear-resistant film containing a solid lubricant.
Item 2. Item 2. The wear-resistant film according to Item 1, wherein a plurality of holes are formed in the plating layer.
Item 3. Item 3. The wear-resistant film according to Item 2, wherein a part or all of the solid lubricant enters the inside of the hole.
Item 4. Item 4. The wear resistance according to any one of Items 1 to 3, wherein the solid lubricant is one or more selected from the group consisting of graphite, molybdenum disulfide, boron nitride, tungsten disulfide, lead oxide, and fluororesin. Film.
Item 5. The wear-resistant film according to any one of Items 1 to 4 and a base material,
The substrate is coated with the wear-resistant coating;
A wear-resistant member in which a surface on the plating layer side of the wear-resistant film is fixed to the substrate.
Item 6. Item 6. The wear-resistant member according to Item 5, wherein unevenness is formed on a surface of the substrate on which the wear-resistant film is coated.
Item 7. A wear-resistant coating and a substrate are provided.
The substrate is coated with the wear-resistant coating;
The abrasion-resistant film includes a plating layer containing molybdenum disulfide,
A wear-resistant member, wherein irregularities are formed on a surface of the base material on which the wear-resistant film is coated.
Item 8. A first step of forming a plating layer by plating the surface of the substrate;
A second step of forming a lubricating layer containing a solid lubricant on the surface of the plating layer;
A method for forming a wear-resistant film comprising:
Item 9. In the plating process of the first step, a plating layer containing resin particles is formed by using a plating solution containing resin particles, and the resin particles are further burnt down by heat-treating the plating layer. Item 9. The forming method according to Item 8.
Item 10. Item 10. The method according to Item 8 or 9, further comprising a step of forming irregularities on the surface of the base material before performing the plating treatment.

  The wear-resistant film according to the present invention can maintain excellent wear resistance over a long period of time even when wear on the slide is repeated, and also has excellent adhesion to the substrate, so that the wear resistance is sustained. Excellent.

  Since the wear-resistant member according to the present invention has the wear-resistant film, the wear-resistant member has excellent wear resistance over a long period of time, and has high adhesion between the substrate and the wear-resistant film. Excellent wear resistance.

  According to the method for forming a wear-resistant film according to the present invention, the method is suitable as a method for producing the wear-resistant film and the wear-resistant member. In particular, the wear-resistant film produced by the method for forming an abrasion-resistant film according to the present invention is likely to continue to have excellent wear resistance over a long period of time because the solid lubricant is easily held in the plating layer. it can.

It is an example of an embodiment of an abrasion-resistant coat of the present invention, and is a schematic sectional view showing the state where it is covered with a substrate. It is an example of other embodiments of an abrasion-resistant coat of the present invention, and is a schematic sectional view showing the state where it is covered with a substrate. It is general | schematic sectional drawing which shows the method of forming the abrasion-resistant film | membrane of this invention on a base material. It is a schematic sectional drawing which shows the other method of forming the abrasion-resistant film | membrane of this invention on a base material. It is a graph which shows the abrasion test result of an Example and a comparative example.

  Hereinafter, embodiments of the present invention will be described in detail.

1. Abrasion Resistant Coating FIG. 1 is a schematic cross-sectional view showing a state in which a substrate is coated with the abrasion resistant coating of the present invention.

  The abrasion-resistant film 10 of the present invention has a plating layer 11 and a lubricating layer 12 laminated on the plating layer 11, and the lubricating layer 12 contains the solid lubricant 2.

  In the embodiment of FIG. 1, the wear-resistant coating 10 is coated on the surface of the substrate 20. A surface of the wear-resistant coating 10 on the plating layer 11 side (a surface opposite to the lubricating layer 12) is fixed to the surface of the base material 20. That is, in the embodiment of FIG. 1, the base material 20, the plating layer 11, and the lubricating layer 12 are laminated in this order. Thereby, the abrasion-resistant member 30 is formed.

  The plating layer 11 is a layer formed by a plating process. The plating layer 11 is a layer formed by a method such as electrolytic plating or electroless plating.

  The plating layer 11 is a layer that can exhibit the role of holding the solid lubricant 2 contained in the lubricating layer 12 in the wear-resistant coating 10. As described later, when the surface of the plating layer 11 has irregularities, the solid lubricant 2 is easily held. Moreover, the retention strength of the solid lubricant 2 can be increased by covering the plating layer 11 having a lower friction coefficient than that of the base material 20 (for example, iron (S45C)).

  Examples of the plating layer 11 include various metal plating layers. The metal that forms the plating layer 11 is not particularly limited. Specific examples of the metal include nickel, copper, chromium, zinc, tin, palladium, lead, silver, gold and the like.

  The metal which forms the plating layer 11 can be only 1 type or 2 types or more. Moreover, the metal which forms the plating layer 11 can also be made into an alloy. Alternatively, the metal forming the plating layer 11 can be an oxide, nitride, sulfide, or the like. Furthermore, the plating layer 11 can include other elements (for example, nonmetallic elements such as phosphorus and boron) as constituent elements in addition to or in place of the metal.

As the plating layer 11, for example, based on metal plating such as Ni, fluororesin (PTFE), mica, alumina (Al ₂ O ₃ ), boron nitride (BN), silicon carbide (SiC), molybdenum disulfide ( The composite plating may be a combination of MoS ₂ ), tungsten disulfide (WS ₂ ), silicon dioxide (SiO ₂ ), or the like.

  Examples of the plating layer 11 include a nickel plating layer (electroless nickel plating layer) formed by electroless plating treatment and an electroless Ni-P composite plating layer. When the plating layer 11 is an electroless Ni—P composite plating layer, the hardness and corrosion resistance of the plating layer 11 can be improved by the effect of the eutectoid P. Moreover, when the plating layer 11 is an electroless Ni-P composite plating layer, it has the advantage that the plating layer 11 of the shape along a base-material shape is easy to be obtained.

  The formation method of the plating layer 11 is not specifically limited, For example, the plating layer 11 can be formed with the well-known various plating method. Hereinafter, the process for forming the plating layer 11 is referred to as “first plating process”.

  As the first plating treatment, for example, electroplating, electroless plating, hot dipping, vapor phase plating, or the like can be performed. The plating process can be either a continuous type or a batch type. As the plating solution used in the first plating treatment, a known plating solution can be used. For example, a plating solution containing various metals including the metal forming the plating layer 11 can be used.

  In electrolytic plating, nickel (Ni), copper (Cu), chromium (Cr), zinc (Zn), tin (Sn), palladium (Pd), lead (Pb), silver (Ag), gold (Au), etc. A plating solution containing one or more metals can be used.

In electroless plating, a plating solution containing Ni—P, Ni—B, Ni—Co, Cu, Ag, or the like can be used. In composite plating, based on Ni plating, fluororesin (PTFE), mica, alumina (Al ₂ O ₃ ), boron nitride (BN), silicon carbide (SiC), molybdenum disulfide (MoS ₂ ), tungsten disulfide (WS) ₂ ), a plating solution containing one or more of silicon dioxide (SiO ₂ ) and the like can be used.

  The thickness of the plating layer 11 is not particularly limited. For example, the thickness of the plating layer 11 can be appropriately set. For example, the thickness is preferably 5 μm or more, and more preferably 5 to 20 μm.

  The surface of the plating layer 11 can be formed flat. Alternatively, the surface of the plating layer 11 is not flat and can be formed to have, for example, irregularities. When the surface of the plating layer 11 has irregularities, the degree of irregularities is not particularly limited as long as the lubricating layer 12 can be laminated on the surface. For example, the unevenness can be formed so that the maximum roughness Rz of the surface of the plating layer 11 is larger than the primary average particle diameter of the lubricating particles described later. In this case, it becomes easy for the plating layer 11 to hold the lubricating particles contained in the lubricating layer 12, the wear resistance of the wear resistant coating 10 is excellent, and the effect is also likely to be sustained. Note that the maximum roughness Rz (μm) in this specification is defined by JIS B 0601: 2001.

  More specifically, the maximum roughness (Rz) of the unevenness on the surface of the plating layer 11 can be about 2 to 5 times the average primary particle diameter of the lubricating particles, for example, 0.01 to 100 μm, 0.1 It can be set to ˜300 μm, more preferably 0.25 to 4 μm, and particularly preferably 0.5 to 2 μm. The unevenness is preferably formed on the entire surface of the plating layer 11 on which at least the lubricating layer 12 is coated, and is preferably formed on the entire surface of the plating layer 11.

  The lubricating layer 12 is a layer formed so as to cover the surface of the plating layer 11 in the wear-resistant coating 10. The lubrication layer 12 is a layer that is positioned on the outermost surface of the wear-resistant coating 10 and can impart wear resistance to the substrate 20 and the like.

  The lubricating layer 12 is a layer containing the solid lubricant 2 as an essential constituent component. The lubricating layer 12 may be a layer formed of only the solid lubricant 2. Alternatively, the lubricating layer 12 may include a material other than the solid lubricant 2. The lubricating layer 12 preferably contains 50% by mass or more of the solid lubricant 2 with respect to the total mass.

  The solid lubricant 2 can be formed of a material that can exhibit wear resistance. For example, a known wear-resistant material and a lubricating material can be used.

Examples of the solid lubricant 2 include graphite (C), molybdenum disulfide (MoS ₂ ), boron nitride (BN), tungsten disulfide (WS ₂ ), lead oxide (PbO), and resin.

  Examples of the resin include a fluorine-based resin. Examples of fluororesins include polytetrafluoroethylene (PTFE), tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer, tetrafluoroethylene-hexafluoropropylene copolymer, polychlorotrifluoroethylene, and tetrafluoroethylene-ethylene copolymer. A coalescence etc. can be mentioned.

  The solid lubricant 2 is preferably formed in the form of particles. In the present specification, the solid lubricant 2 formed in the form of particles is particularly referred to as “lubricated particles”. When the solid lubricant 2 is a lubricant particle, the adhesion of the solid lubricant 2 to the plating layer 11 is increased, so that the adhesion of the lubricant layer 12 is improved. Moreover, when the hole mentioned later is formed in the plating layer 11, it becomes easy for a lubricating particle to enter into this hole.

  The average primary particle diameter of the lubricating particles is not particularly limited. From the viewpoint that it is easy to enter the later described holes formed in the plated layer 11 and that a plurality of lubricating particles easily enter one hole, it is preferably smaller than the diameter of the hole described later, and formed on the surface of the plated layer 11. It is preferable that the roughness is smaller than the Rz. Further, the lubricating particles are preferably smaller than the average primary particle diameter of resin particles described later. For example, the average primary particle diameter of the lubricating particles can be set to 0.5 to 2 μm. The average primary particle diameter of the lubricating particles refers to a value measured with a particle size distribution measuring machine using a dynamic light scattering method.

  The lubricating particles can be in various shapes other than spherical, elliptical, and flat.

  The lubricant particles are particularly preferably molybdenum disulfide particles. Molybdenum disulfide has a layered crystal structure with good sliding properties and is a particle with excellent load resistance, so that it has excellent wear resistance of the formed wear-resistant coating 10 and has its wear-resistant member. The durability of the wear resistance effect is also easily improved, and it is easy to adhere to the surface of the plating layer 11 and to enter the hole. From this viewpoint, it is preferable that the lubricating layer 12 be formed only of molybdenum disulfide particles.

  The lubricating layer 12 can cover the entire surface or a part of the plating layer 11. For example, the lubricating layer 12 preferably covers 50% or more of the surface of the plating layer 11, and preferably covers 100% (that is, the entire surface).

  The thickness of the lubricating layer 12 is not particularly limited. For example, the thickness of the lubricating layer 12 can be 1 to 30 μm.

  The method for forming the lubricating layer 12 is not particularly limited. Hereinafter, the method for forming the lubricating layer 12 is referred to as “lubricating layer forming means”.

  Examples of the lubricating layer forming means include known means such as shot blasting, barreling, painting, coating, imprinting (imprinting) using a raw material containing the solid lubricant 2. The raw material containing the solid lubricant 2 used in the lubricating layer forming means can be composed only of the solid lubricant 2. Here, shot blasting means that particles are accelerated and collide with an object, and does not necessarily mean that a shot blasting device or the like is used.

  The lubricating layer 12 can be formed such that its surface has irregularities. Alternatively, the lubricating layer 12 can be formed so that the surface thereof is flat. Even when the surface of the lubricating layer 12 has irregularities, it can be gradually flattened by wear. That is, when the wear resistant film 10 is continuously used, the surface of the lubricating layer 12 is also flattened. When flattened, the conformability of the lubricating layer 12 can be improved.

  FIG. 2 is a schematic cross-sectional view showing a state in which a base material is coated with a wear-resistant film according to another embodiment of the present invention.

  2 has a plating layer 11 and a lubricating layer 12 laminated on the plating layer 11, and the lubricating layer 12 contains the solid lubricant 2. This is the same as the embodiment.

  In the wear resistant coating 10 in the form of FIG. 2, a plurality of holes 15 are formed in the plating layer 11. In other words, the plating layer 11 has a porous (porous) shape. This point is different from the abrasion-resistant film 10 of the embodiment of FIG. In the embodiment of FIG. 2, the same configuration as that of the embodiment of FIG. 1 can be adopted except that a plurality of holes 15 are formed in the plating layer 11.

  When the plurality of holes 15 are formed in the plating layer 11 as in the embodiment of FIG. 2, the solid lubricant 2 contained in the lubricating layer 12 can enter the holes 15, and the lubricating layer 12 and the plating are formed. The adhesion of the layer 11 is improved. Further, even if the solid lubricant 2 contained in the lubricating layer 12 enters the holes 15 and the lubricating layer 12 existing on the surface is peeled off due to wear, the solid lubricant 2 that has entered the holes 15 is removed from the plating layer 11. Is hard to fall off. Thereby, the wear resistance of the wear-resistant coating 10 can be maintained for a longer period. When the solid lubricant 2 is a lubricating particle, the wear resistance effect of the wear-resistant coating 10 is particularly easily maintained because it is easily held in the holes 15.

  The plurality of holes 15 formed in the plating layer 11 are preferably distributed over the entire region of the plating layer 11. That is, the plurality of holes 15 are preferably formed not only on the surface layer of the plating layer 11 but also inside the plating layer 11. In this case, even if the surface of the plating layer 11 is shaved due to wear, the internal hole 15 appears from the shaved portion, and the solid lubricant 2 remaining on the surface can enter the hole 15. As a result, the wear resistance can be maintained by the solid lubricant 2, and the effect of the wear resistance can be maintained for a longer period.

  The content rate of the hole in the plating layer 11 is not specifically limited. For example, the holes are preferably present in the plating layer 11 in a proportion of 30 to 70% by volume. The volume ratio of the holes present in the plating layer 11 can be obtained by measuring the volume ratio of the resin particles contained in the plating layer 11 in the second forming method described later. In the second forming method, the volume ratio of the resin particles contained in the plating layer 11 is calculated, for example, by dissolving the plating layer 11 in a solvent and taking out only the resin particles, and calculating the volume from the weight of the obtained resin particles. Can be measured.

  It is preferable that the hole 15 has a size that allows the solid lubricant 2 to enter. In particular, when the solid lubricant 2 is the lubricating particles, the holes 15 preferably have a diameter that is twice or more the average primary particle diameter of the lubricating particles. The diameter of the hole 15 here refers to the surface or cross-section of the plating layer 11 by direct observation with a transmission electron microscope, randomly select 50 holes 15 and measure the equivalent circle diameter. This is the arithmetic average value.

  In the embodiment of FIG. 2, it is preferable that a part or all of the solid lubricant 2 included in the lubricating layer 12 enters the inside of the hole 15 formed in the plating layer 11. In this case, the solid lubricant 2 is less likely to fall off due to wear, and the wear resistance effect can be maintained for a long time. The solid lubricant 2 may enter the hole 15 from the initial state, and may gradually enter the hole 15 by repeated use and wear.

  In particular, it is preferable that a plurality of lubricating particles enter one hole 15. In this case, it is easy to prevent the lubricant particles from falling off and to prevent the plating layer 11 from peeling off. However, it is preferable that a space remains inside the hole 15. In this case, even if the wear-resistant coating 10 is in a reduced pressure state, there is an advantage that the wear-resistant coating 10 is difficult to peel off.

  The holes 15 may be colored. Since the hole 15 is colored, the hole 15 can be visually discriminated.

  The holes 15 are preferably formed so as not to penetrate the plating layer 11 in the thickness direction. When the hole 15 is formed without penetrating the plating layer 11 in the thickness direction, the through hole does not reach the base material 20, so that the corrosion resistance of the wear-resistant film due to so-called plating defects (cracks, pinholes) is prevented. The decrease can be suppressed.

  The method for forming the plating layer 1 having the holes 15 is not particularly limited. Hereinafter, a method of forming the plating layer 1 having the holes 15 is referred to as a “hole forming method”.

  Examples of the hole forming method include a method in which the plating solution used in the first plating process for forming the plating layer 11 contains resin particles and the plating layer 11 is formed using the resin particles.

  The kind of the plating solution containing resin particles is the same as the plating solution used in the first forming method, except that the resin solution contains resin particles.

  The plating layer 11 formed from the plating solution containing resin particles contains resin particles. Holes 15 can be formed in the plating layer 11 by heat-treating the plating layer 11 to burn off the resin particles. The hole 15 can be formed in a portion where the resin particles existed before the heat treatment.

  The kind of resin particle is not particularly limited. For example, at least one resin particle selected from the group consisting of acrylic resin particles and polyester resin that evaporates at 350 ° C. or higher can be exemplified.

  The average primary particle diameter of the resin particles is not particularly limited. For example, if the solid lubricant 2 is a lubricating particle, it is preferable that the average primary particle diameter is 2 to 5 times the average primary particle diameter of the lubricating particle.

  From another viewpoint, the average primary particle diameter of the resin particles can be made larger than the maximum roughness Rz of the surface of the plating layer 11. In this case, the lubricating particles easily enter the holes 15 formed after the resin particles are burned out, and the lubricating particles are easily held in the holes 15, so that the wear resistance is easily improved.

  In still another aspect, the average primary particle diameter of the resin particles can be made equal to or less than the maximum roughness Rz of the surface of the plating layer 11. In this case, irregularities are likely to be present on the surface of the plating layer 11, and the irregularities are likely to appear particularly when the surface is worn, so that the wear resistance is improved. For example, the average primary particle diameter of the resin particles can be 1 μm or more and 10 μm or less.

  The plating solution containing the resin particles preferably contains a surfactant. In this case, the dispersibility of the resin particles in the plating solution is improved, and the resin particles are easily dispersed uniformly in the formed plating layer 11. As a result, the holes 15 formed in the plating layer 11 are easily distributed uniformly.

  The kind of surfactant is not specifically limited. For example, a known anionic, cationic or nonionic surfactant can be used.

  As for the usage-amount of surfactant, 0.5 to 2.0 weight% of surfactant can be used with respect to the resin particle, for example.

  The conditions for the heat treatment of the plating layer 11 containing the resin particles are not particularly limited. For example, the heating temperature can be 300 to 350 ° C. The heating time can be appropriately changed according to the heating temperature, and can be, for example, 120 to 300 minutes. The heating conditions are not limited, and heating can be performed under various atmospheres such as an atmosphere of an inert gas such as nitrogen or an air atmosphere. Heat treatment can be performed by a commercially available heating furnace or the like.

  Another example of the hole forming method is an electrolytic plating method such as a porous nickel plating method. In addition, the holes 15 can be formed by a method of roughening the surface of the plating layer 11 formed by the first plating process by an appropriate method such as shot blasting or etching.

  In the embodiment of FIG. 2, the other configuration can be the same as that of the embodiment of FIG. 1 except that holes 15 are formed in the plating layer 11 and lubricating particles can enter the holes 15.

  The wear-resistant film 10 of the present invention can have, for example, the forms shown in FIGS. 1 and 2 and can be suitably used for various members as a film for imparting wear resistance. The wear resistant member 30 described later can be formed. When various members are coated with the wear-resistant film 10 of the present invention, as shown in FIGS. 1 and 2, the wear-resistant film 10 is coated so that the lubricating layer 12 is located on the surface side.

  The wear-resistant film 10 of the present invention can provide high wear resistance by including the lubricating layer 12 having excellent wear resistance, and also has good adhesion between the lubricating layer 12 and the plating layer 11. Yes, even if wear is repeated, the effect of wear resistance is not easily lost.

  In particular, when the hole 15 is formed in the plating layer 11 as in the embodiment of FIG. 2, the solid lubricant 2 contained in the lubricating layer 12 is easily held by the plating layer 11. Can last for a long time. When the solid lubricant 2 is a lubricating particle, the effect becomes particularly remarkable.

  Since the conventional abrasion-resistant film is peeled off as it continues to be worn, the abrasion resistance can gradually disappear, but the abrasion-resistant film 10 of the present invention has the above-described configuration. The effect of wear resistance can be maintained for a longer period than before.

2. As shown in FIGS. 1 and 2, the wear-resistant member 30 of the present invention includes a wear-resistant coating 10 and a substrate 20, and the substrate 20 is the wear-resistant coating 10. The surface of the plating layer side 11 of the wear-resistant coating 10 is fixed to the substrate 20.

  The abrasion-resistant coating 10 has the same configuration as that described in “1. Abrasion-resistant member” of this specification.

  Various solid materials can be applied to the base material 20, and the type is not particularly limited. For example, various materials such as metals, alloys, resins, ceramics, paper, wood, and cloth can be used as the substrate 20.

  The shape of the base material 20 is not particularly limited. For example, examples of the shape of the base material 20 include a substrate shape, a film shape, a rod shape, a block shape, a spherical shape, an elliptic spherical shape, and a distorted shape. The base material 20 may be various sliding parts, machine parts, tools, dies, and the like.

  It is preferable that irregularities are formed on the surface of the substrate 20 on which the wear-resistant coating 10 is coated. In this case, the adhesion between the wear-resistant coating 10 and the substrate 20 can be particularly improved. As a result, even if wear is repeated, the wear resistance effect is not easily lost, and the wear resistance effect can be maintained for a longer period of time.

  The maximum roughness (Rz) of the unevenness formed on the substrate 20 is not particularly limited. For example, the maximum roughness (Rz) of the irregularities formed on the substrate 20 can be about 2 to 5 times the average primary particle diameter of the lubricating particles. Specifically, the maximum roughness of the unevenness formed on the substrate 20 is preferably 0.25 to 4 μm, and more preferably 0.5 to 2 μm. The irregularities are preferably formed on at least the entire surface of the substrate 20 on which the wear-resistant coating 10 is coated, and are preferably formed on the entire surface of the substrate 20.

  The surface of the plating layer side 11 of the wear-resistant coating 10 can be directly fixed to the substrate 20. Alternatively, another layer may be interposed between the surface on the plating layer side 11 of the wear-resistant film 10 and the base material 20, so that the wear-resistant film 10 can be fixed to the base material 20.

  The wear-resistant member 30 of the present invention is provided with the wear-resistant film 10 so that excellent wear resistance can be maintained over a long period of time even if wear is repeated.

  In the wear-resistant member 30, a part or all of the solid lubricant contained in the lubricating layer 12 may enter the inside of the hole 15 formed in the plating layer 11.

  As another form of the wear-resistant member according to the present invention, a wear-resistant film and a base material are provided, the base material is covered with the wear-resistant film, and the wear-resistant film contains molybdenum disulfide. It is also possible to mention a form (hereinafter sometimes referred to as “third form”) in which the plating layer is provided and the surface of the base material on which the wear-resistant film is coated is formed with irregularities.

  In the third embodiment, the wear-resistant film is not formed with a lubricating layer, and is formed, for example, only with a plating layer containing molybdenum disulfide. The solid lubricant is the same as in the embodiment of FIG.

  The plating layer of the third form can be formed using, for example, a plating solution used in the first plating process containing molybdenum disulfide. Except for the point that molybdenum disulfide is contained in the plating solution, the type of the plating solution can be the same as the plating solution used in the first plating treatment.

  Also in the third embodiment, holes 15 may be formed in the plating layer 11. The holes 15 can be formed by a method similar to the above-described hole forming method.

  Even in the wear-resistant member 30 of the third embodiment, since the adhesion between the wear-resistant film 10 and the base material 20 is high, even if the wear is repeated, the effect of wear resistance is not easily lost, and it is longer. The wear resistance effect can be maintained over the entire range.

3. Method for Forming Abrasion Resistant Film The method for forming the abrasion resistant film 10 is not particularly limited, and the abrasion resistant film 10 can be produced by various methods as long as the above-described configuration is provided. Hereinafter, as an example, a method of forming the wear-resistant coating 10 in the form of FIG. 1 on the base material 20 (hereinafter referred to as “first forming method”) and an abrasion-resistant coating 10 in the form of FIG. Will be described on the base material 20 (hereinafter referred to as “second forming method”).

(First forming method)
The method for forming the abrasion-resistant coating 10 includes a first step of forming the plating layer 11 by plating the surface of the base material 20, and the formation of the lubricating layer 12 containing the solid lubricant 2 on the surface of the plating layer 11. And a second step.

  FIG. 3 is a schematic explanatory view of the first forming method.

  The configuration of the base material 20 shown in FIG. 3A is the same as that of the base material 20 described in “2. Wear-resistant member”.

  As shown in FIG.3 (b), before performing the plating process in a 1st process, the process of forming an unevenness | corrugation on the surface of the base material 20 can also be further provided. In this case, the abrasion-resistant film 10 is formed on the uneven surface formed on the surface of the substrate 20, and the wear-resistant member 30 including the substrate 20 having the uneven surface is obtained.

  The method for forming irregularities on the surface of the substrate 20 is not particularly limited. For example, irregularities can be formed on the surface of the substrate 20 by a known means. Specifically, unevenness can be formed on the surface of the base material 20 by subjecting the surface of the base material 20 to treatment such as shot blasting, shot peening, and etching.

  As a method of forming irregularities on the surface of the substrate 20, it is particularly preferable to use shot blasting. By adopting shot blasting, it is easy to adjust the maximum roughness (Rz) of the surface of the base material 20 to a desired range, and the processed surface tends to have a satin shape in which continuous irregularities are deeply formed. The unevenness is preferably formed on the entire surface of the substrate 20 on which at least the wear-resistant coating 10 is coated, and is preferably formed on the entire surface of the substrate 20.

  The plating process in the first step is the same as the first plating process.

  In the first step, when irregularities are formed on the surface of the substrate 20, irregularities may also be formed on the surface of the plating layer 11 formed by the first plating process. The unevenness | corrugation formed in the base material 20 can be made into the aspect similar to the unevenness | corrugation demonstrated in embodiment of FIG.

  In the first step, the plating layer 11 is laminated on the base material 20 as shown in FIG.

  In the second step, the lubricating layer 12 containing the solid lubricant 2 is laminated on the surface of the plating layer 11 formed in the first step.

  In the second step, the lubricating layer 12 can be formed by the aforementioned lubricating layer forming means. Thereby, as shown in FIG. 3D, the lubricating layer 12 containing the solid lubricant 2 is laminated on the plating layer 11. When the surface of the plating layer 11 is uneven, the surface of the lubricating layer 12 immediately after formation can also be uneven.

  When the lubricating layer 12 is formed of lubricating particles, lubricating layer forming means is suitable. In particular, by employing means such as shot blasting, the lubricating particles are likely to adhere to the surface of the plating layer 11 by physical action. As a result, the lubricating layer 12 having a large adhesive force can be formed on the plating layer 11. Moreover, when unevenness | corrugation is formed in the base-material 20 surface using shot blast in a 1st process, it is preferable to use shot blast also for the method of laminating | lubricating the lubricating layer 12. FIG.

  The wear-resistant film having the form shown in FIG. 1 can be formed on the substrate 20 by the forming method including the first step and the second step. According to such a forming method, an abrasion-resistant film can be easily formed.

(Second forming method)
FIG. 4 is a schematic explanatory view of the second forming method.

The second forming method is the first forming method. In the plating process of the first step, a plating solution containing resin particles is used to form a plating layer containing resin particles, and the plating layer is heat-treated. This further includes a step of burning out the resin particles. In the second forming method, a plurality of holes are formed in the plating layer in the second forming method in which the resin particles are burned out by heat treatment. It is the same method.

  In FIG. 4, as an example, a first plating process is performed using a plating solution containing the resin particles to form a plating layer 11 (FIG. 4B), and the resin particles 5 are formed by performing the heat treatment. The form (FIG.4 (c)) which burns down and forms the hole 15 is shown. In FIG. 4, the resin particles 5 correspond to the resin particles.

  In the second formation method, the heat treatment can be performed between the first step and the second step, as shown in FIG. Alternatively, heat treatment can be performed after the second step. However, in terms of the fact that the solid lubricant 2 easily enters the holes 15, the heat treatment is performed between the first step and the second step, that is, the resin particles in the first step as shown in FIG. It is preferable to perform heat treatment after forming the plating layer 11 to be contained and before forming the lubricating layer 12.

  When the heat treatment is performed before forming the lubricating layer 12, the hole 15 can be colored after the heat treatment is performed to form the holes 15. As a coloring method, for example, a known coloring method can be adopted, and a known method such as applying a colorant such as ink or paint can be exemplified.

  In the second forming method, the method for forming the unevenness on the base material 20 and the method for forming the lubricating layer 12 are the same as the first forming method.

  In the second forming method, the method of forming the lubricating layer 12 preferably employs shot blasting. In this case, the solid lubricant 2 easily enters the holes 15. Further, according to shot blasting, the lubricating particles are fixed to the plating layer 11 by the action of a physical external force. Therefore, it is easy to put lubricating particles into the surface of the plating layer 11 and the holes 15.

  In particular, when the diameter of the hole 15 increases toward the inside of the plating layer 11 (in the case where the opening cross-sectional area of the hole 15 is larger than the surface of the plating layer 11), if the hole 15 is inserted by shot blasting, the inside of the hole 15 is further increased. Lubricating particles can easily enter the holes 15. As a result, the lubricating particles are less likely to fall off the plating layer 11, and the wear resistance effect can be maintained for a longer period of time.

  By the second forming method described above, the wear-resistant film having the form shown in FIG. 2, that is, the wear-resistant film 10 including the plating layer 11 in which the plurality of holes 15 are formed is formed on the base material 20.

  In the method of forming the holes 15 in the plating layer 11 using 5 resin particles, the holes 15 having a large aspect ratio are easily formed, and steep irregularities are easily formed. Thereby, the solid lubricant 2 such as lubricating particles is easily held in the plating layer 11, and it is easy to form the wear-resistant film 10 that is excellent in durability of wear resistance.

  According to the method for forming a wear-resistant film according to the present invention, the method is suitable as a method for producing the wear-resistant film and the wear-resistant member. In particular, the wear-resistant film produced by the method for forming an abrasion-resistant film according to the present invention is likely to continue to have excellent wear resistance over a long period of time because the solid lubricant is easily held in the plating layer. it can.

  The method of the present invention, the wear-resistant coating 10 and the wear-resistant member 30 can be suitably used for various members. Examples of applicable members include various machine parts, power system parts such as sliding bearings and piston rings of various engine parts, continuously operating power transmission parts such as chains, tools, molds, etc. Various sliding parts such as those used for household goods, industrial machines, transport equipment or leisure goods are also exemplified.

  EXAMPLES Hereinafter, although an Example demonstrates this invention more concretely, this invention is not limited to the aspect of these Examples.

Example 1
Iron (S45C) was prepared as a base material, and irregularities were formed on the base material by shot blasting. For shot blasting, a ceramic projection material (alumina, garnet) is used, the sand grid is mesh size # 100 to 150, the pressure is 10 kgf / cm ^2, and the maximum roughness Rz of the irregularities on the substrate surface is 2 to 2. The thickness was 4 μm.

  Next, electroless Ni-P plating treatment was performed on the substrate on which the irregularities were formed. As the electroless Ni plating solution, “Nimuden KTB (registered trademark)” (Uemura Kogyo Co., Ltd.) was used, and the other working environment was in accordance with the standard conditions of the plating solution. The thickness of the produced plating layer was 10 μm.

  Next, molybdenum disulfide particles (average primary particle diameter of 1 μm) were retained on the plating layer by shot blasting to form a lubricating layer having a thickness of about 3 μm. Thus, the base material coat | covered with the abrasion-resistant film was obtained as an abrasion-resistant member.

(Example 2)
Iron (S45C) was prepared as a base material, and unevenness was formed on the base material by shot blasting. For shot blasting, a ceramic projection material (alumina, garnet) is used, the sand grid is # 100 to 150, the pressure is 10 kgf / cm ^2, and the maximum roughness Rz of the irregularities on the substrate surface is 2 to 4 μm. did.

  Next, electroless Ni-P plating treatment was performed on the substrate on which the irregularities were formed. As the electroless Ni plating solution, “Nimden KTB (registered trademark)” (Uemura Kogyo Co., Ltd.) is used, and acrylic resin particles having an average primary particle size of 2.5 μm are further added to this plating solution in an amount of 5 g / L. In addition, a small amount of a cationic surfactant was added. Other working environments were in accordance with the standard conditions of the above plating solution. The generated plating layer had a thickness of 10 μm and contained acrylic resin particles inside.

  Thus, the base material in which the plating layer was formed was heat-processed at 350 degreeC for 120 minutes. As a result, the acrylic resin particles were burned out and holes were formed in the plating layer.

  Next, molybdenum disulfide particles (average primary particle diameter: 1 μm) were retained on the plated layer in which the holes were formed by shot blasting to form a lubricating layer having a thickness of about 3 μm. Thus, the base material coat | covered with the abrasion-resistant film was obtained as an abrasion-resistant member.

(Example 3)
Iron (S45C) was prepared as a base material, and unevenness was formed on the base material by shot blasting. For shot blasting, a ceramic projection material (alumina, garnet) is used, the sand grid is # 100 to 150, the pressure is 10 kgf / cm ^2, and the maximum roughness Rz of the irregularities on the substrate surface is 2 to 4 μm. did.

  Next, electroless Ni-P plating treatment was performed on the substrate on which the irregularities were formed. As the electroless Ni plating solution, “Nimuden KTB (registered trademark)” (Uemura Kogyo Co., Ltd.) is used, and molybdenum disulfide particles (average primary particle diameter 1 μm) are further added to this plating solution in an amount of 5 g / L. Added. Other working environments were in accordance with the standard conditions of the above plating solution. The generated plating layer had a thickness of 10 μm and contained molybdenum disulfide particles inside. Thus, the base material coat | covered with the abrasion-resistant film was obtained as an abrasion-resistant member.

(Example 4)
A wear resistant member was obtained in the same manner as in Example 2 except that the substrate was not uneven.

(Comparative Example 1)
In Example 1, a plating layer and a lubricating layer were not formed, and a base material on which irregularities were formed was obtained as a comparative sample.

(Comparative Example 2)
In Example 1, a lubricating layer (molybdenum disulfide particles) having a thickness of about 3 μm was formed directly on the substrate without forming a plating layer, and this was obtained as an abrasion resistant member.

(Comparative Example 3)
A wear resistant member was obtained in the same manner as in Example 1 except that the lubricating layer was not formed.

(Comparative Example 4)
A wear-resistant member was obtained in the same manner as in Example 3 except that biotite (average primary particle size of 1 μm or less) was used in place of molybdenum disulfide particles and a cationic surfactant was added to the plating solution. It was.

(Comparative Example 5)
A wear-resistant member was obtained in the same manner as in Example 3 except that PTFE particles (average primary particle size of 1 μm or less) were used instead of molybdenum disulfide particles.

(Abrasion resistance test)
The wear resistance test of the wear resistant member was performed under the following conditions.
・ Load: 10N
-Partner material: Stainless steel-Number of revolutions: The wear-resistant member was 100 rpm, and the partner material was 100 rpm.
・ Abrasion time: Conducted until the coating disappears. ・ Measures the amount of abrasion of the coating every 15 minutes from the start of measurement. The abrasion resistance test can be performed using a pin-on-disk type abrasion tester.

  In FIG. 5, the result of the abrasion resistance test of the abrasion resistant member obtained by each Example and the comparative example is shown. From this figure, it can be seen that the wear-resistant members obtained in the examples are less likely to increase in wear amount even if the wear-resistance test is performed for a long time, whereas the wear-resistant members of the comparative examples are It can be seen that the amount of wear increases significantly immediately after the start of measurement or after a certain period of time. As a result, it can be said that the wear-resistant members obtained in the examples can maintain excellent wear resistance over a long period of time even if wear is repeated.

  In Comparative Examples 1 and 2, it was found that the plating layer 12 was not present and peeling due to wear occurred immediately. Comparative Example 2 was not worn while the initial molybdenum disulfide was present, but at the same time as the molybdenum disulfide disappeared from the surface, the material was immediately worn.

  In Comparative Example 3, since there is a plating layer, it is difficult to wear at the initial stage, but it seems that the plating layer 12 gradually disappears and wear has progressed.

  The composite plating of Comparative Examples 4 and 5 is good because the amount of wear is small in the initial stage due to the effect of the composite particles, but the progress of wear is fast in the latter half, and all the coatings wear out in about 60 to 90 minutes. I have reached the material.

  On the other hand, Examples 1-4 were good results. In particular, Example 2 resulted in the least amount of wear due to wear time. Example 2 is considered to be because the plating layer is formed porous and has holes.

  In Example 1, since molybdenum disulfide is inserted and fixed in the uneven portion of the plating layer, the wear resistance can be maintained for a long period of time.

  In Example 2, since the molybdenum disulfide is put in the hole 15, the lubricating layer is firmly fixed, and as a result, the wear resistance is excellent.

  Example 3 is different from Examples 1 and 2, because molybdenum disulfide is held in the plating layer, so that it has slidability and is firmly fixed to the plating layer. As a result, Example 3 showed better abrasion resistance than Comparative Examples 4 and 5 as a composite plating layer.

  In Example 4, since there was no uneven treatment of the substrate 15, the adhesion between the base material 15 and the plating layer was not as high as in the other examples, but had higher wear resistance than the comparative example.

2: Solid lubricant 5: Resin particles 10: Abrasion resistant coating 11: Plating layer 12: Lubricating layer 13: Coat layer 15: Hole 20: Base material 30: Abrasion resistant member

Claims (10)

Having a plating layer and a lubricating layer laminated on the plating layer;
The lubricating layer is a wear-resistant film containing a solid lubricant.   The abrasion-resistant film according to claim 1, wherein a plurality of holes are formed in the plating layer.   The wear-resistant coating film according to claim 2, wherein a part or all of the solid lubricant enters the inside of the hole.   The said solid lubricant is 1 or more types chosen from the group which consists of graphite, molybdenum disulfide, boron nitride, tungsten disulfide, lead oxide, and a fluororesin, The anti-resistance of any one of Claims 1-3. Abrasion film. A wear-resistant film according to any one of claims 1 to 4 and a base material,
The substrate is coated with the wear-resistant coating;
A wear-resistant member in which a surface on the plating layer side of the wear-resistant film is fixed to the substrate.   The wear-resistant member according to claim 5, wherein irregularities are formed on a surface of the base material on which the wear-resistant film is coated. A wear-resistant coating and a substrate are provided.
The substrate is coated with the wear-resistant coating;
The abrasion-resistant film includes a plating layer containing molybdenum disulfide,
A wear-resistant member, wherein irregularities are formed on a surface of the base material on which the wear-resistant film is coated. A first step of forming a plating layer by plating the surface of the substrate;
A second step of forming a lubricating layer containing a solid lubricant on the surface of the plating layer;
A method for forming a wear-resistant film comprising:   In the plating process of the first step, a plating layer containing resin particles is formed by using a plating solution containing resin particles, and the resin particles are further burnt down by heat-treating the plating layer. The forming method according to claim 8.   The forming method according to claim 8, further comprising a step of forming irregularities on the surface of the base material before performing the plating treatment.